Hara Masaki, Handzlik Gabriela, Arczyński Mirosław, Iwasaki Takanori, Pinkowicz Dawid, Nozaki Kyoko
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Kraków 30-387, Poland.
Inorg Chem. 2025 Jun 30;64(25):12540-12547. doi: 10.1021/acs.inorgchem.5c00532. Epub 2025 Jun 16.
In the recent development of homoleptic σ-hydrocarbyl rare-earth metal complexes focusing on reactivity and catalytic activity, rare-earth metal complexes with a variety of alkyl ligands have been synthesized, and the principle for designing thermally stable σ-hydrocarbyl rare-earth metal complexes has been established. Nevertheless, there has been no report of homoleptic rare-earth metal complexes comprising only identical bidentate σ-hydrocarbyl ligands. Herein, we present homoleptic σ-hydrocarbyl rare-earth metal complexes possessing bidentate biaryldiyl ligands, tris(biphenyl-2,2'-diyl)yttrium(III) complex , tris(1,1'-binaphthyl-2,2'-diyl)yttrium(III) complex , and tris(1,1'-binaphthyl-2,2'-diyl)erbium(III) complex . Single-crystal X-ray crystallography revealed the trigonal prismatic geometry of , along with the trigonal antiprismatic geometry of and , each constructed through three-centered two-electron bonds among the rare-earth metal, -carbon, and lithium. The static and dynamic magnetic properties of were investigated in the solid state, showing a slow magnetic relaxation typical of single-molecule magnets. The fitting of the magnetic behavior of and the theoretical calculations indicated that the magnetic relaxation of occurs primarily through a Raman relaxation process.
在近期围绕反应性和催化活性开展的均配型σ-烃基稀土金属配合物的研究进展中，已合成出具有多种烷基配体的稀土金属配合物，并确立了设计热稳定σ-烃基稀土金属配合物的原则。然而，尚无仅由相同双齿σ-烃基配体组成的均配型稀土金属配合物的相关报道。在此，我们展示了具有双齿联芳二基配体的均配型σ-烃基稀土金属配合物、三（联苯-2,2'-二基）钇（III）配合物、三（1,1'-联萘-2,2'-二基）钇（III）配合物以及三（1,1'-联萘-2,2'-二基）铒（III）配合物。单晶X射线晶体学揭示了的三角棱柱几何结构，以及和的三角反棱柱几何结构，它们各自通过稀土金属、碳和锂之间的三中心双电子键构建而成。对的静态和动态磁性进行了固态研究，显示出单分子磁体典型的慢磁弛豫。对和的磁行为拟合以及理论计算表明，的磁弛豫主要通过拉曼弛豫过程发生。
